Polymerization products of perfluoroalkylalkylmonocarboxylic acid esters

ABSTRACT

Homo- and Copolymers of monomeric perfluoralkylalkylmonocarboxylic acid esters are provided which esters are derived from acyclic aliphatic epoxides. These esters contain at least one perfluoroalkyl radical with 4 to 14 carbon atoms which is bonded over an alkylene group with 1 to 10 carbon atoms to a carboxyl group, which in turn is bonded in an esterlike manner to an acyclic radical. This radical contains in the 2-position to the ester bridge an optionally etherified or esterified hydroxyl group; said radical is bonded via an ester, ether or carbamate bridge to an alkenyl group with 2 to 3 carbon atoms which is optionally linked via a second ester, ether or carbamate bridge to an acyclic radical which in turn may be bonded via an ester bridge and an alkylene group to a perfluoroalkyl radical. The homo- and copolymers with other polymerisable products are used to achieve oleophobic furnishes on porous or non-porous substrates, especially on fibrous materials, such as textiles and papers.

United States Patent [191 J tiger [451 Aug. 26, 1975 [75] Inventor:Horst Jiiger, Bettingen, Switzerland [73] Assignee: Ciba-Geigy AG,Basel, Switzerland [22] Filed: Dec. 20, 1973 [21] Appl. No.: 427,277

Related U.S. Application Data [62] Division of Ser. No. 112,445, Feb. 3,1971, Pat. No.

[51] Int. Cl. C08f 3/52; C08f 3/62; C08f 3/64 [58] Field of Search.....260/89.5 H, 89.5 N, 86.1 R, 260/86.1 N, 86.1 E, 89.1, 85.7, 87.3, 86.7,

[56] References Cited UNITED STATES PATENTS 3,575,940 4/1971 Katsushimaet al..... 260/89.5 H 3,624,139 ll/1971 Davis et a1. 260/89.5 H

3,825,575 7/1974 Jager 260/408 Primary ExaminerHarry Wong, Jr. Attorney,Agent, or FirmJoseph G. Kolodny; Prabodh I. Almaula; Edward McC. Roberts[5 7] ABSTRACT Homoand Copolymers of monomericperfluoralkylalkylmonocarboxylic acid esters are provided which estersare-derived from acyclic aliphatic epoxides. These esters contain atleast one perfluoroalkyl radical with 4 to 14 carbon atoms which isbonded over an alkylene group with l to 10 carbon atoms to a carboxylgroup, which in turn is bonded in an ester-like manner to an acyclicradical. This radical contains in the 2- position to the ester bridge anoptionally etherified or esterified hydroxyl group; said radical isbonded via an ester, ether or carbamate bridge to an alkenyl group with2 to 3 carbon atoms which is optionally linked via a second ester, etheror carbamate bridge to an acyclic radical which in turn may be bondedvia an ester bridge and an alkylene group to a perfluoroalkyl radical.

The homoand copolymers with other polymerisable products are used toachieve oleophobic furnishes on porous or non-porous substrates,especially on fibrous materials, such as textiles and papers.

14 Claims, No Drawings .1 I POLYMER IZA TION PRQDUCTS OF IPERFLUOROALKYLALKYLMONOCARBQXYLIC ACID ESTERS i cRoss REFERENCE Thisapplication is a division of applicants copending application Ser. No.112,445, filed Feb. 3, 1971 now US. Pat. No. 3,825,575, which issued onJuly 23, 1974.

The subject of the invention are perfluoroalkylalkylmonocarboxylic acidesters which contain a) at least one perfluoroalkyl radical with 4 to 14carbon atoms,

which is bonded via an alkylene group with l to 10 carbon atoms to acarboxyl group, which is bonded in an ester-like manner to b) anacyclic, aliphatic radical which is substituted in the 2-position to theester bridge by an optionally etherified or esterified hydroxyl group,this radical being bonded, via an ester, ether or carbamate bridge, toc) an alkenyl group with 2 to 3 carbon atoms, which is optionally linkedvia a second ester, ether or ,carbamate bridge to a radical like b),which is in turn bonded via an ester bridge to a radical like a). Thealkylene group, via which the-perfluoroalkyl radical is bonded to thecarboxyl group,-'can be acyclic branched or unbranched or cyc.lic. Theacyclic radicals contain 1 to 10 carbon atoms, whilst the cycloalkyleneradicals possess 5 or 6 ring ,carbon atoms. The ethylene, n-butylene,n-decylene, isopropyleneor cyclohexylene radical may be mentioned asexamples.

Preferably, these perfluoroalkylalkylmonocarboxylic acid esterscorrespond to the formula wherein R and R each denote a perfluoroalkylradical with 4 to 14 carbon atoms, Q and Q each denote an acyclicalkylene radical with l to carbon atoms or a cycloalkylene radical with5 or 6 ring carbon atoms, A and A each denote'an alkyl radicalwhich isoptionally substituted further, E and E each denote a radical of theformula I OOC:, O or -OOC NY'-, wherein Y represents a hydrogen atom ora lower alkyl radical, G denotes a radical of the formula 2 wherein Xrepresents a hydrogen atom or a methyl radical, and n denotes l or 2,and the hydroxyl group is in the 2-position relative to the RCOO or R'-COO- group. I

' Further suitable compounds are the perfluoroalkylalkylmonocarboxylicacid esters of the formula wherein the symbols R, R, A, A, E, E, G and nhave the indicated meaning and p and q each denote an integer having avalue of l to 10, preferably 2 to 6.

Thus, where n is l, the compounds of the formula (I) are esters with twoperfluoroalkylalkylmonocarboxylic 0 acid radicals, and if n is 2, theyare esters with only one perfluoroalkylalkylmonocarboxylic acid esterradical. The radical G can be bonded by its two free valencies,optionally to E or E or to H, that is to say in the case of n 2 EG-H canrepresent the radical of, for

- example, methacrylic, acrylic or crotonic acid, and in the case of nl, -E-G E. can represent the radical of for example maleic, itaconic-orcitraconic acid. However, perfluoroalkylalkylmonocarboxylic acid esterswith only one perfluoroalkyl radical are preferred, that is to saycompounds of the formula V wherein R, *A, E, G and p have the indicatedmeaning, and the hydroxyl group is inthe 2-position to the R- COO--group.

Compounds of particular interest are perfluoroalkylalkylmonocarboxylicacid esters of the formula wherein R, E, G and p have the indicatedmeaning, A,

, denotesa hydrogen atom 'oran alkyl radical, A denotes an alkyl radicaland m denotes l or 2.

A preferred position is then occupied by per;

fluoroalkylalkylmonocarboxylic acid ejstei s of the for';

mula

wherein R, A, A,,1A E, X, pand m have the indicated meaning. and thehydroxyl group is in the 2-position to the RCOO group. Advantageousproperties are above all also shown by perfluoroalkylalkylmonocarboxylicacid esters of the formula l (Vll) d wherein R, G, p and m have theindicated meaning, and A denotes a hydrogen atom, an alkyl radical withl to 8 carbon atoms and A, denotes an alkylene radical with l to 8carbon atoms. i

Perfluroalkylalkylmonocarboxylic acid esters of the formula wherein R, AX and p have the indicated meaning and A represents a hydrogen atom or amethyl or ethyl group, are particularly suitable.

Good results are further also achieved withperfluoroalkylalkylmonocarboxylic acid esters of the formula l 1.However, n-perfluoroalkyl radicals are preferred. A

further possibility as a perfluoroalk'yl radical is also a- (VIII) vwherein r represents an integer having a value of l to V l l (Xlu) OHCH;

(Xlb) I CHgOH CH5 The perfluoroalkylalkylmonocarboxylic acid esters.

according to the invention are manufactured according to methods whichare in themselves known, by reacting (l aperfluoroalkylalkylmonocarboxylic acid, which contains a perfluoroalkylradical with 4 to l4 carbon atoms, which is bonded via an alkylenebridgewith l to 10 carbon atoms or a cycloalkylene bridge with 5 or 6 ringcarbon atoms to the carb'oxyl group, with (2) an acyclic, aliphaticepoxide, which is bonded via an ester, ether or carbamate bridge to analkenyl group with 2 to 3 carbon atoms, which-is optionally linked via asecond ester, etheror carbamate bridge to an acyclic, aliphatic epoxide,and optionally further carrying out an etherification or esterificationwith an aliphatic compound.

Perfluoroalkylalkylmonocarboxylic acid esters of the formulae (I) and(ll) are obtained by the reaction of the component (1) with (2), anepoxide of the formula wherein A, A' E, E, G and n have the indicatedmeanmg.

Perfluoroalkylalkylmonocarboxyli'c acid esters of the Formula.(lll)areobtained' an epoxide of the formula wherein A, E and G have theindicated meaning, is used as'component (2).

' The particularly interesting compounds of the formula (IV) areobtained if an epoxide of the formula wherein A, A E. G and-m have theindicated mean-i ing, is used as component (2').

If an epoxide of the formula (XVI) wherein A A A O and X have theindicated meaning, are employed as component (2).

Glycidyl methacrylate has proved a particularly advantageous component(2).l'nstead of the epoxides, the corresponding diols can also be usedfor the manufacture of the compounds according to the invention.

The .perfluoroalkylalkylmonocarboxylic acids employed as component lpreferably contain 5 to ll, or especially 7 to 9, carbon atoms in theperfluoroalkyl radical.

The perfluoroalkyl radical'is preferably bonded to the carboxyl groupvia an alkylene bridge me'mber with 2 to 6 carbon atoms.

The reaction to manufacture the perfluoroall tylalkylmonocarboxylic acidesters according "to the invention is appropriately carried out in an,organic solvent-for example ethyl acetate. As a rule, the reaction isalso carried out in the presence of a catalyst, for example anhydroussodium acetate.'Preferably, the reaction is carried out at a temperatureof to 70Cand especially 40 to 60C. Depending'on the reaction temperatureand the reactivity of the components (1) and "(2) employed, the reactiontakes 1 to 24, or espee'ially4'to 8, hours. The reaction mixturesoptionally, also contain stabilisers for the alkenyl group with 2 'to 3'carbon atoms, such as, for example, hydroquinonemono'me'thyl-ether. 5

The acyclic, aliphaticradical which is bondedto theperfluoroalkylalkylmonocarboxylic acid and to the alkenyl group with 2to 3icarbo'n atoms, that is to say'the' radical A in the formulae (I)and (ll), is for examp'le derived from an epoxyalkanol,l I such as 2-epoxypropanol-l, "or from an epoxyhalogenoalkane, such asepichlorohydrin. Both types of compound can be easily manufactured fromolefines, for example ally alcohol or allyl chloride, by epoxidation. iFurther possible epoxyalkanols are, for example: 9- epoxyoctadecanolll'-epoxyoctanol-3, lepoxyoctanoI-4, l-epoxy-4-methylhexanol-4, 2-epoxy-S-methylheptanol-S, l-epoxy-5-methylpentanol-4, 4- epoxypentanol-l3-epoxypentanol-4.

The olefinic groups can for example be introduced by means of thefollowing compounds:'acr'ylic acid, methacrylic acid, crotonic acid,maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylamide'.methacrylamide, vinyl chloride and ally] isocyanate.

Another process of arriving at the perfluoroalkylalkylmonocarboxylicacid esters in question consist of esterifying (l) aperfluoroalkylalkylmonocarboxylic acid for its acid halide with (2) ahydroxyalkyl-vinyl compound, (3) epoxidising the vinyl group andsubsequently (4) esterifying the product, for example with anethylenically unsaturated carboxylic acid.

Further, it is also. possible to obtain theperfluoroalkylalkylmonocarboxylic acid .esters according to theinvention if (.1) a perfluoroalkylalkylcarboxylic acid is firstesterified with (2) a hydroxyhalogenohydrin, (3) the product isconverted into the epoxide, hydrogen halide being split off, andthereafter(4)' the epoxide is esterified with, for example, anethylenically unsaturated carboxylic acid. I

The corresponding ethers or; amides are manufactured analogouslyinaccordance with the latter two methods. I

vIf one of these latter two processes are used, wherein theperfluoroalkylalkylmonocarboxylic acid is first reacted withan acyclicaliphatic compound and only subsequently etherified or esterified, it isalso possible to obtain products which are additionally furtheresterified or etherified at the hydroxyl group which is in the positionadjacent to the perfluoroalkylalkylcarboxylic acid ester group. w

The perfluoroalkylalkylmonocarboxylic acid esters according to theinvention can, by vi'rtue'of their vinyl group, be homopolyr nerised, or,copolymerised with other ethylenically unsaturated copolymerisablecompounds. 1 1 v The polymerisation of the monomericperfluoroalkylalkylmonocarboxylic"acid esters can take place in solutionor in emulsion, and in the presence of catalysts which release freeradicals or act by an ionic mechanism, the ester being polymerisedbyitself, with anotherprefluoroalkylalkylmonocarboxylic acidesteraccordiii'g to the inventibn, oi-with other polymerisable compoundsto give linear polymers. Thefollowing are suitable for copolymerisationwith the perfluoroalkylalkylmonocarboxylic acid estersz' a. Vinylestersof organic carboxylic acids, fo'r example vinyl ac etate, vinyl;formate,- vinyl butyrate or (vinyl benzoate, V e Y K b.' 'vinyl alkyl'ket one s and"vinyl'alkyl ethers, such as vinyl methyl ketone andvinylbutyl ether, v *"c; vinyl halides, such as vinyl chloride, vinylfluoride or vinyl idene chloride, ,d. vinyl aryl compounds, such' asstyrene and substituted "styrenes i H v i v lei.derivatives'bf'theacrylic acid series, such as acrylonitrileo'racrylamide and; preferably, its derivatives which are substituted at theamide nitrogen,

7 such as N-methylolacrylamide, I N- methylolacrylamide-alkyl-ether,N,N- dihydroxyethylacrylamide, N-tert.-butylacrylamide andhexamethylolmelaminetriacrylamide,

f. esters of the acrylic acid series, such as esters of acrylic acid,methacrylic acid, a-chloroacrylic acid, crotonic acid, maleic acid,fumaric acidor itaconic acid, and monoalcohols or dialcohols with l to18 carbon atoms or phenols, for example ethyl acrylate, glycidylacrylate, butyl acrylatc, acrylic acid monoglycol ester or dodecylacrylate, and

g. polymerisable olefines, such as isobutylene, butadiene or2-chlorobutadiene.

h. Polymers, such as for example polyolefines, onto which the monomericcompounds are grafted and polymerised (graft copolymers).

Preferably used compounds are esters, amides or methylolamides ofacrylic acid or methacrylic acid, such as acrylic acid ethyl ester,acrylic acid butyl ester, acrylic acid glycidyl ester, glycolmonoacrylate, and also calcium acrylate, acrylamide, methylmethacrylate,acrylamide, methacrylamide, N-methylolacrylamide,N-methylolacrylamide-rnethyhether and N-tert. butylacrylamide; vinylesters of organic carboxylic acids, such as vinyl acetate; styrene,vinyl halides, such as vinyl chloride or.vinylidene chloride, orpolymerisable olefines, such as isobutylene.

The polymers as a rule consist of 5 to 100 percent by weight of aperfluoroalkylalkylmonocarboxylic acid ester and of 95 to percent byweight of another compound. Particularly interesting technicalproperties are shown by those polymers which contain to 30, preferably 8to 20, percent by weight of the monomericperfluoroalkylalkylmonocarboxylic acid ester, calculated relative to thetotal weight of the monomer unit, in a copolymerised form. Amongst thesepolymers, the binary or ternary copolymers which in addition to 5 to 30percent by weight of the perfluoroalkylalkylmonocarboxylic acid esteralso contain an acrylic acid ester, such as butyl acetate, andoptionally a third monomer, especially a vinyl ester, such as vinylacetate, in a copolymerised form, are in turn distinguished by speciallyadvantageous technical properties, particularly in the field of textilefinishing.

The manufacture of the polymers by homopolymerisation orcopolymerisation of perfluoroalkylalkylmonocarboxylic acid esters withone or more other copolymerisable ethylenically unsaturated monomers iscarried out according to customary methods, for example by blockpolymerisation, bead polymerisation, polymerisation in aqueous emulsionor preferably by solvent polymerisation in an organic solvent which issuitable for this purpose, such as, for example, acetone,

benzene, sym'.- dichloroethane or ethyl acetate.

The polymerisation is appropriately carried out with warming, preferablyto the boiling point of the solvent, and with the addition of catalystswhich act by an ionic mechanism or of peroxidic or other catalysts whichyield free radicals and are soluble in the reaction medium,'such as forexample benzoyl peroxide, lauroyl peroxide or01,01'-azoisobutyrodinitrile.

Depending on the nature of the polymerisation conditions and of themonomeric starting substances used, the polymeric compounds arc obtainedin the form of viscous solutions, of granules or in theform ofemulsions.

It is furthermore also possible to carry out the polymerisation of themonomeric compounds in the presence of substrates. It can for example becarried out on glassfibre fabrics or on textile material. In this case,the substrate in question is appropriately impregnated with solutions oremulsions of the monomers, and thereafter the polymerisation is carriedout by heating the material, a polymerisation catalyst being added.

Because of the presence of free hydroxyl groups, the monomericperfluoroalkylalkylmonocarboxylic acid esters and their polymers reactwith compounds which contain several functional groups capable ofreaction with hydroxyl groups, such as 1,2-epoxide groups, isocyanategroups, acrylyl groups, methylol groups, methylol groups etherified withlower alcohols, aldehyde groups or easilyhydrolysable ester groups, andthe like. Such polyfunctional compounds are therefore suitable for useas crosslinking components or curing components for the copolymers,containing hydroxyl groups, according to the invention. A

As such crosslinking components there may especially be mentioned:epoxide compounds, namely polyglycidyl ethers such as butanedioldiglycidyl ether and diglycidyl ether, diisocyanates andpolyisocyanates, such as o-, mand p-phenylenediisocyanate, toluylene-2,4-diisocyanate and l,5-naphthylenediisocyanate; acrylyl compounds,such as methylenebis-acrylamide and symmetricaltriacrylylperhydrotriazine; poly(2,3- dihydro-l,4-pyranyl) compounds,such as (2,3- dihydro-l, 4-pyran-2-yl)-methyl ester; aldehydes, such asformaldehyde or glyoxal, and soluble phenolformaldehyde condensationproducts, such as novolacs or resols. Aminoplasts which are soluble inwater or in organic solvents are preferentially used as crosslinkingcomponents. Possible aminoplasts are formaldehyde condensation productsof urea, thiourea, guanidine, ac'etylenediurea and dicyandiamide, andalso of aminotriazines'such as' melamine or of guanamines, such asacetoguanamine, benzoguanamine, ,tetrahydrobenaddition to the etherradicals, the condensation products can also additionally containradicals of highermolecular acids, such as, for example, stearic acid..

Particularly good technical results in the field of textile finishingare obtained on using water-soluble condensation products offormaldehyde and melamine or especially the esterification product oretherification product of hexamethylolmelamine-methyl-ether and stearicacid or stearyl alcohol, as crosslinking components. v i

The homopolymers 'and copolymers of theperfluoroalkylalkylmonocarboxylic acid esters can also be used as amixture with polymers not containing fluorine (so-called extenders).Very suitable polymers not containing fluorine are here, for example,the homopolymers of acrylic acid esters or methacrylic acid esters,suchas poly(ethyl acrylate) or copolymers of acrylic acid esters ormethacrylic acid esters with methylolacrylamide ormethylolmethacrylamide. The perfluoroalkylalkylmonocarboxylic acidesters according to the invention can be used either as such, or ashomopolymers or copolymers, for the treatment of porous or. non-poroussubstrates, and preferably for the production of oleophobic finishes onthese.

Leather, or especially fibre materials, such as textiles and paper, maybe mentioned as poroussubstrates. Metal and especially glass are aboveall relevant nonporous substrates.

Simultaneously with the action of imparting an oleophobic effect, theseperfluoro compounds also show hydrophilic properties. For imparting anoleophobic effect, the substrates can be treated either with solutionsor dispersions or emulsions of the monomeric or polymeric perfluorocompounds. The monomers can for example be applied to the textilematerial from a so lution in an organic solvent, and be fixed thermallyto the fabric after evaporation of the solvent. Polymers can also beapplied to the fabrics from suitable solvents.

Possible textile materials which are preferably treated with themonomeric or polymeric perfluoro compounds are for example those ofnatural or regenerated cellulose, such as cotton, linen or rayon,viscose staple or cellulose acetate. However, textiles of wool,synthetic polyamides, polyesters or polyacrylonitrile can also betreated. Mixed woven fabrics or mixed knitted fabrics of cottonpolyester fibres can also advantageously be finished. The textile s canin these cases be in the form of filaments, fibres or flocks, butpreferably of woven fabrics or knitted fabrics.

Preparations which contain the monomeric or polymeric perfluorocompounds can be applied to the substrate in the usual manner which isin itself known. Woven fabrics can for example be impregnated by theexhaustion process or on a padder which is charged with the preparationat room temperature. The impregnated material is thereafter dried at 60to 120C and subsequently optionally still subjected to a heat treatmentat above 100C, for example at l20 to 200C.

Preparations which in addition to the perfluoro cornpounds according tothe invention also contain components with hydrophobic properties, forexample solutions or emulsions of fatty acid condensation products, forexample with aminoplast precondensates, or paraffin emulsions, producean oil-repellent effect on the substrates treated therewith, coupledwith a waterrepellent effect.

Further, a so-called soil release" and anti-soiling" effect can also beachieved with the perfluoro compounds according to the invention,especially on cotton.

EXAMPLE 1 content is The solution is concentrated in vacuo at 30C. Theresidue is taken up in 100 ml of diethyl ether and washed 3 times withml of water, and yields a clear, viscous phase. Weight, 23.7 g 55.25% ortheory. a

The structure is confirmed by recording a mass spectrum, in that thisshows a molecular weight of 584, which corresponds to a product of theformula 2 g of the end product according to Example 1 are dissolved in10 ml of ethyl acetate. 0.1 g of potassium persulphate was additionallyadded to this solution, and the mixture was heated to C, for 10 minutes,whilst stirring. The resulting polymer has a solids content of 19.52%.

EXAMPLE 3 28.4 g of glycidyl methacrylate together with 100 g ofperfluoroalkylalkylcarboxylic acid and l g of sodium acetate (anhydrous)and 0.5 g of hydroquinonemonomethyl-ether as a stabiliser, are dissolvedin 300 ml of ethyl acetate. After 4 hoursreaction at C, the ethylacetate is removed in vacuo, the residue is taken up in diethyl ether,the solution is eluted 3 times with 20 ml of water and dried with sodiumsulphate, and the diethyl ether is removed in vacuo.

66.7 g of alightbiown, waxy substance are corresponding to a yieldof'52.6%.

The structure is confirmed by recording a mass spectrum, in that thisshows molecular weights of 634, 662 and 734, which correspondsto astructure of the'formula obtained,

HO- ci CH5 n=5,7,9;m=2,4 v l. The perfluoroalkylalkylcarboxylic acidused has the following composition according to he'gas chromatogram andmass spectrum:

8% of C F C H CooH 2. In a rep eat'of the above example, a perfluoroalkylalkylcarboxylic acid of the following'composition was used. The yieldwas 91.3% of theory.

40.5% of C F C H COOH M 592 15% of c,.,F,.c,H,,co0H M 620 EXAMPLE 4 Thestructure is confirmed by recording a mass spectrum, in that this showsmolecular weights of 749, 677

and 777, which corresponds to a structure of the formula n 5,7,9,ll m2,4,6 I

1. The perfluoroalkylalkylcarboxylic acid used has 15 EXAMPLE 5 g ofperfluoroalkylalkylcarboxylic acid glycerine monoester (manufacturedfrom perfluoroalkylalkylcarboxylic acid" and glycerine-glycid) and 0.1 gof hydroquinone monomethyl ether are dissolved in 50 ml of ethylacetate. 2.6 g of fumaric acid chloride dissolved in 20 ml of ethylacetate are added dropwise. The reaction is maintained at 50C overnight, the ethyl acetate is removed in vacuo, the residue is taken up indiethyl ether, the solution is washed with bicarbonate until neutral,and dried, and the ether is removed in vacuo. Yield: 15.8 g 74.2% of alight brown product.

The structure of the compound according to the formula n 5,7,9,l l m=-2,4,6" is confirmed by recording a mass spectrum.

1. The perfluoroalkylalkylcarboxylic acid used for the preparation hasthe same'composition as in Example 4.

EXAMPLE 6 trum shows molecular weights of 646, 746 and 846 and confirmsthe following structure;

[CFACFQH (CH2)",COO

1. The following perfluoroalkylundecylic acid was used for thepreparation of the ester.

EXAMPLE 7 14.2 g of glycidyl methacrylate, 60.4 g of aperfluoroalkylcyclohexylcarboxylic acid" and 2.0 g of anhydrous sodiumacetate are dissolved in 400 ml of ethyl acetate, and the reaction iscarried out as described in Example 3.

The yield is 39.7 g 53.22% of theory.

Recording a mass spectrum shows molecular weights of 588, 688 and 788and permits confirmation of the following structure of the compounds:

I OH CH:

l. The following perfluoroalkylcyclohexylcarboxylic acid was used forthe preparation of the ester:

28% 0t cmcm, COOH M 446 47.3% of cF,(cF,) 'O M 546 18.5% of CF (CF2)9@ M646 EXAMPLE 8 A solution of 1.6 parts of N-methylolmethacrylamide methylether and 38.4 parts of the compound from Example 3, in parts ofacetone, is heated to the boil whilst stirring and passing nitrogen overthe mixture. The solution is treated 7 times, at intervals of 2 hours,with a solution of, in each case, 0.4 part of azodiisobutyronitrile in 4parts of acetone. Polymerisation is al lowed to go to completion over afurther 10 hours at the reflux temperature, and about 132 parts of a 31%strength solution are obtained, corresponding to a polymer yield ofEXAMPLE 9 a 30% strength solution of the ride is"pr'epared I EXAMPLEWoven pieces of cotton, cotton-polyester, synthetic polyamide, polyesterand wool gaberdine are successively dipped into'the polymer solutionmanufactured according to Example 2, and thus impregnated with theperfluoro compound. I

- A piece of filter paper isalso impregnated in this way, and a piece ofglass isalso coated. The samples of fabric, glass and paper arethereafter dried "for 10 minutes The assessment of the oil-repellenteffect is carried out according to the so-called 3 M oil repellency test(Crajeck and Petersen, Textile Research Journal32, 320-331 .1960] usingheptane-Nujol mixtures. in the assessment, l 50 denotes the bestachievable rating. The individual samples are assessed immediately afterdrying, that is to say as obtained, after an SNV-4 wash 1 machine washfor 30 minutes at 95C, at a liquor ratio of 1:50, in a bath which perlitre contains 5 g'of soap and 2 g of calcined sodium carbonate and atotal of 1-0 steel balls) and after a wash'for 5 minutes in boilingtrichloroethylene. Theresu'lts are summarised in the table below.

polymer in benzotrifluo machine wash for 30 minutes at 60C, at a liquor.ratio of 1:50, in a washing liquor which per litre contains 5 g of soapand 2 g of anhydrous sodium carbonate).

The cotton-polyester fabric which has been finished with the liquor D,is additionally also tested for its soil release properties. For thispurpose, the test specimen is spotted with synthetic skin grease(Spangler, Cross and Sohaafma, J. Am. Oil. Soc. 42, 723 (1965)) andNujol. The spots are applied before the first SNV-3 wash, and areassessed,after washing, with ratings from 1 to 5. The rating 1 denotesnot washed out" and the rating 5 denotes completely washed out." For thesoil release test, rating 5 is the'best rating.

B fi

I C D F .Cotton, as obtained 60V 80 l l0 120 90 70 l X SNV 3 7 0 7 120 v70 6O 5 X SNV-3 100 100 l0 X SN\/3 70- Cotton/polyester. v v as obtained60 80 100 I 1 [O 80 60 l X SNV-3 80 l00 70 5 X SNV-3 100 90 I0 X SNV-3Soil release Nujol l X SNV-3- 3.5

Skin grease l X SNV-3 2.5

I claim:

The following liquors are preparedfromithe products of Examples 3 to 9:

Constituents. Liquor Product from C Example 8 Example 3 Example 4Example 9 Poly(oc tyl methacrylate) 30 Example 6 Example 7 Chloroaceticacid 3 3 3 Water v v Ethanol- Dioxane Acetone! but-unol, -l :4Chloroform Concentrations in gll Hexumethylolmelaminc-pentamethyl-ethcrl. Polymerisation products consisting of homopolymers of at least oneperfluoroalkylalkylmonocarboxylic acid esters of the formula formula orI OOCNY,' 7 wherein Y represents a hydrogen atom or a lower alkylradical, G denotes a radical of the formula wherein X represents ahydrogen atom or a methyl radical, and n denotes l or 2, and thehydroxyl group is in the 2-posit-ion relative to the RQCOO or R-Q 1 -COOgroup.

2. Polymerisation products according to claim 1, ofperfluoroalkylalkylmonocarboxylic acid esters of the formula wherein thehydroxyl group is in the two-position relative to the R(CH ),,COO-group, and p and q each denote an integer having a value of l to 10.

3. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters wherein p and q are eachintegers having a value of 2 to 6.

4. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula 5. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula wherein A denotes a hydrogen atom or an alkyl radical, and Adenotes an alkylene radical and m denotes or 2.

6. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula wherein the hydroxyl group is in the 2-position relative to theR-(CH ),,COO- group.

7. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula 8. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula wherein A denotes a hydrogen atom or an alkyl radical with l to8 carbon atoms and A, denotes an alkylene radical with l to 8 carbonatoms.

9. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula A represents a hydrogen atom or a methyl or ethyl group.

10. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula 14. Process for the manufacture of polymerisation productsaccording to claim 1, wherein the monomericperfluoroalkylalkylmonocarboxylic acid esters are polymerised insolution or in emulsion in the presence of radical or ionic catalysts.

e'sters-

1. POLYMERISATION PRODUCTS CONSISTING OF HOMOPOLYMERS OF AT LEAST ONEPERFLUOROALKYLALKYLMONOCARBOXYLIC ACID ESTERS OF THE FORMULA 2.Polymerisation products according to claim 1, ofperfluoroalkylalkylmonocarboxylic acid esters of the formula 3.Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters wherein p and q are eachintegers having a value of 2 to
 6. 4. Polymerisation products accordingto claim 2, of perfluoroalkylalkylmonocarboxylic acid esters whichcorrespond to the formula
 5. Polymerisation products according to claim2, of perfluoroalkylalkylmonocarboxylic acid esters which correspond tothe formula
 6. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula
 7. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula
 8. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula
 9. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula
 10. Polymerisation products according to claim 2, ofperfluoroalkylalkylmonocarboxylic acid esters which correspond to theformula
 11. Polymerisation products according to claim 1, ofperfluoroalkylalkylmonocarboxylic acid esters which contain aperfluoroalkyl radical with 5 to 11 carbon atoms.
 12. Polymerisationproducts according to claim 11, of perfluoroalkylalkylmonocarboxylicacid esters which contain a perfluoroalkyl radical with 7 to 9 carbonatoms.
 13. Polymerisation products according to claim 1, ofperfluoroalkylalkylmonocarboxylic acid esters of the formula
 14. Processfor the manufacture of polymerisation products according to claim 1,wherein the monomeric perfluoroalkylalkylmonocarboxylic acid esters arepolymerised in solution or in emulsion in the presence of radical orionic catalysts.